ScienceDirect. Tuning the optical and rheological properties of host-guest systems based on an epoxy acrylate and MMA

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1 Available online at ScienceDirect Procedia Technology 15 (214 ) nd International Conference on System-Integrated Intelligence: Challenges for Product and Production Engineering Tuning the optical and rheological properties of host-guest systems based on an epoxy acrylate and MMA Uwe Gleißner a *, Kirsten Honnef a and Thomas Hanemann a,b a First affiliation, Address, City and Postcode, Country b Second affiliation, Address, City and Postcode, Country Abstract Polymers with individually adjusted optical and rheological properties are gaining more and more importance in industrial applications like information technologies and for biological use. With respect to the aspired applications the refractive index n of a matrix polymer has to be adjusted. For a refractive index increase an electron-rich organic dopant like phenanthrene is added to a commercially available reactive polymer based resin (epoxy acrylate). For a refractive index reduction hexafluorobutyl methacrylate is added to a different MMA-based resin. Changes in viscosity for applications like ink-jet printing can be achieved by using a comonomer with suitable properties. As a result of the investigation the change in viscosity went from 47 Pa s (pure resin) down to 4 mpa s (pure difunctional monomer). Adding phenanthrene to the pure epoxy acrylate based polymer matrix the refractive index increased linearly with dopant concentration. For a decreasing refractive index a change from 1.49 down to 1.42 was obtained. 214 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license Peer-review ( under responsibility of the Organizing Committee of SysInt 214. Peer-review under responsibility of the Organizing Committee of SysInt 214. Keywords: Refractive index adjustment; optical polymers; polymer waveguides * Corresponding author. Tel.: Tel.: ; fax: address: The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license ( Peer-review under responsibility of the Organizing Committee of SysInt 214. doi:1.116/j.protcy

2 162 Uwe Gleißner et al. / Procedia Technology 15 ( 214 ) Introduction Optical polymers are becoming more and more important since the market for microoptical components is growing steadily. This is based on the demand of the automotive sector, the use for telecom applications, optical disks and functional films for liquid crystal displays [1-4]. * Corresponding author. Tel.: ; fax: address: A modification of the optical properties like the refractive index can help reducing coupling losses e.g. between waveguides and active semiconductor optical devices like LEDs or laser diodes. These losses at an interface of two different materials due to reflections are so called Fresnel reflections or Fresnel losses. They can be calculated using equation 1. [5] n1 n R n1 n (1) The smaller the differences between n1 and n2 are the less damping losses occur at the interface. Since waveguides are also used in N N coupling elements and cable connectors [6], total reflectance inside the waveguide is necessary. For this purpose in a 1 μm monomode waveguide the difference between the two refractive indices of cladding and core has to be around.5 [7]. According to these examples a high demand for optical materials with an adjustable refractive index exists. For different shaping methods like ink-jet and offset printing adjusting viscosity retaining the aspired optical properties is one of the main issues. Furthermore, offset and inkjet printing is relatively cheap and capable of mass production. Ink-jet printing needs viscosity values around 5 to 1 mpa s whereas offset printing needs a viscosity of around 2 mpa s respectively. By choosing suitable monomers and additives an individual adjustment of the pre polymer viscosity is possible. 2. Experimental 2.1. Materials The first used matrix polymer Syntholux (Synthopol) is a commercially available UV-curable mixture based on an epoxy acrylate diluted with 8 % TPGDA (tripropylene glycol diacrylate). For the viscosity adjustment ethylene glycol dimethacrylate (EGDMA) and phenanthrene as a dopant for refractive index rise were applied. The second mixture, Plexit 55 a commercially available reactive resin based on 3 % PMMA solved in MMA, was used as a polymer matrix. For refractive index drop hexafluorobutyl methacrylate (HFBMA) was added as dopant. Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide was used as UV sensitive photo initiator, dilauroyl peroxide was applied as a thermal initiator Measurement setup The mixture s viscosity was quantified by a cone and plate rheometer (CVO5, Bohlin). In a first measurement setup the temperature was increased from 2 C to 8 C whereas the shear rate was kept constant at 6 1/s. In a second setup the temperature was set at 2 C, 4 C and 6 C and the shear rate was increased at each temperature from 1 to 2 1/s. The refractive indices were measured at a wavelength of 589 nm at 2 C using an Abbe refractometer (DR- M2/155, ATAGO). From every mixture two samples were produced and measured five times each.

3 Uwe Gleißner et al. / Procedia Technology 15 ( 214 ) Mixture and sample preparation All starting materials were put together and then mixed using a high-speed disperser (Ultra-Turrax, IKA) with up to 3. rpm under ambient conditions. The mixtures were dispersed up to one minute to achieve a good homogenization. Test samples for refractive index measurements were produced using a silicon mold between two glass plates. To prevent the test samples from sticking to the glass plates fluorine ethylene propylene (FEP)-foil was placed between the silicon mold and the glass plates. After irradiation with a high power LED unit (LED Spot 1, Dr. Hönle AG) at a wavelength of 45 nm the samples were heated up in an oven at 8 C to achieve full polymerization. As a heating and cooling rate 5 K/min were used to minimize thermal stress. First, seven mixtures were made of Syntholux, diluted with, 1, 2, 4, 6, 8, and 1 wt% EGDMA. Second, phenanthrene was added with 5 and 1 wt% to the mixtures which contained and 2 wt% EGDMA and with 15 wt% to the mixture with 4 wt% EGDMA respectively. However, 1 and 15 wt% of phenanthrene have been close to the solubility limit of the mixture. Additionally, both 3 wt% photo initiator and.5 wt% thermal initiator were added. All above mentioned mixtures are shown in table 1. Third, four mixtures were made out of the second polymer, Plexit55, with, 5, 9, and 1 % hexafluorobutyl methacrylate (HFBMA). Table 1. Summary of mixtures with Syntholux. Syntholux / wt% EGDMA / wt% Phenanthrene / wt% Results and discussion 3.1. Flow behavior The viscosity of the mixtures depends strongly on the content of EGDMA and weakly of the content of phenanthrene and is independent of the shear rate in the measured range. As one can see in figure 1 (left) this measurement was performed at 2 C. The same measurement performed at 4 and 6 C got results with the same order but with a clearly lower viscosity of course. The highest viscosity was reached by the mixture of pure Syntholux and the lowest viscosity was reached by the mixture of pure EGDMA, whereas the small values were measured at the clear resolution limit of the used rheometer. Table 2 shows the results of highest and lowest viscosities reached at different temperatures. As stated above the viscosity of Syntholux and EGDMA mixtures depends strongly on the temperature as it is also shown in figure 1 (right). The viscosity drops with increasing temperature. Again the highest viscosity was

4 164 Uwe Gleißner et al. / Procedia Technology 15 ( 214 ) reached by the mixture of pure Syntholux with around 48 Pa s at 2 C and.18 Pa s at 8 C. The lowest viscosity was also again reached by the mixture of pure EGDMA with around 4 mpa s at 2 C and around 1 to 2 mpa s at 8 C. Again, these values mark the resolution limit of the rheometer. Regarding the influence of the used dopant phenanthrene for adjusting refractive index on viscosity (figure 2 (left) and (right)) it can be seen that phenanthrene lowers the viscosity independent of the shear rate. Fig 1. (left) viscosity of mixtures out of Syntholux and EGDMA depending on EGDMA-content and shear rate at 2 C; (right) viscosity depending on EGDMA-content and temperature at a shear rate of 6 1/s. Table 2. Highest and lowest viscosity values. Viscosity Temperature / C Syntholux / wt% EGDMA / wt% 48 Pa s 4 Pa s.6 Pa s 4 mpa s mpa s mpa s 6 1 At 2 C the mixture with wt% phenanthrene has a viscosity of around 2 Pa s, whereas the mixture with 5 wt% phenanthrene shows a viscosity of 1.9 Pa s. 1 wt% phenanthrene lowers the viscosity to 1.55 Pa s. A decrease also occurs at 4 and 6 C (figure 2 (left)). Figure 2 (right) shows that decrease of viscosity due to phenanthrene is independent of temperature. As a main result it is possible to adjust the viscosity in a wide range for different shaping methods like inkjet or offset printing Optical properties Despite the fact that EGDMA decreases viscosity of the pre polymer it also decreases the refractive index of the mixtures and thus the refractive index of the polymerized samples (figure 3). Starting with a liquid refractive index of 1.53 for pure Syntholux the refractive index decreases with the content of EGDMA and ends with for pure EGDMA. The decline is approximately linear from 1 to 1 wt% EGDMA. The refractive index of the polymerized samples starts at 1.55 for pure Syntholux and ends at for pure EGDMA respectively. The decline is, in contrast to the liquid values, nonlinear. The gap in refractive indices between liquid pre polymers and polymerized samples increases with the content of EGDMA. It starts with a delta n =.2 for pure Syntholux and ends with a delta n =.55. That implies that EGDMA changes its refractive index during polymerization stronger

5 Uwe Gleißner et al. / Procedia Technology 15 ( 214 ) than Syntholux. With 2 wt% EGDMA the refractive index with a value of is still very close to pure Syntholux. That means that the refractive indices of the samples increased the more during polymerization the more EGDMA they contained. Fig 2. (left) viscosity of mixtures out of Syntholux, EGDMA and phenanthrene depending on phenanthrene content and shear rate; (right) viscosity depending on phenanthrene content and temperature. To compensate the decreased refractive index due to the adjustment of viscosity, phenanthrene was added to the mixtures up to the solubility limit. Adding phenanthrene increased the refractive index of the pre polymer mixtures (fig. 4 (left)) linearly up to the solubility limit. The solubility limit of the mixtures with and 2 wt% EGDMA was around 1 wt%. In case of the mixture with 4 wt% EGDMA the solubility limit of phenanthrene was 15 wt% respectively. Regarding the polymerized samples adding phenanthrene to the mixtures increased the refractive index dependent on the content of EGDMA. With the pure Syntholux mixture it was possible to achieve a difference of the refractive index of.12 with a maximum at 1.562, with the 2 wt% EGDMA mixture a difference of.17 and a maximum of and with the 4 wt% EGDMA mixture a difference of.18 and a maximum refractive index of was measured respectively.

6 166 Uwe Gleißner et al. / Procedia Technology 15 ( 214 ) Fig 3. (left) refractive index of liquid pre polymers out of Syntholux, EGDMA and phenanthrene; (right) refractive index of polymerized samples out of Syntholux, EGDMA and phenanthrene. Fig 4. (left) refractive index of liquid pre polymers and polymerized samples out of mixtures containing Syntholux and ethylene glycol dimethacrylate; (right) refractive index of polymerized samples out of Plexit55 and HFBMA. In general it is possible to increase the refractive index and moreover to compensate decreasing refractive indices due to viscosity adjustment. On the opposite of increasing refractive indices it is also possible to decrease it with the right choice of dopants. In this case HFBMA was chosen because of its low refractive index. The addition to Plexit55 reduced the refractive index by a wide margin as it can be seen in figure 4 (right). Starting with n = for pure Plexit55 the refractive index falls down to a value of for pure HFBMA, whereas a mixture of 9 wt% HFBMA has almost the same refractive index with a value of Given the huge step of.75 for the refractive index which is possible with HFBMA, it is very suitable as material for producing waveguides with a huge step of refractive index between core and cladding. 4. Summary As a result of the investigation of EGDMA on Syntholux the change in viscosity went from 48 Pa s (pure resin) to 4 mpa s (pure EGDMA), which is a more suitable region for inkjet printing. However, the refractive index decreased at the same time from to Adding phenanthrene to the pure Syntholux the refractive index increased from up to and for the 2 wt% EGDMA mixture the lowered refractive index increased from

7 Uwe Gleißner et al. / Procedia Technology 15 ( 214 ) up to Following this it is possible to compensate a decreasing refractive index due to viscosity adjustment. Even more it is possible to exceed these values to enable waveguides which are only produced out of the above mentioned material compositions. As a result of the investigation for a decreasing refractive index, a change from 1.49 (pure MMA resin) to 1.42 (pure hexafluorobutyl methacrylate) was obtained. It was successfully shown that both, viscosity and refractive index can be adjusted in a wide range depending on the given requirements. Acknowledgements The authors gratefully acknowledge the financial support by Deutsche Forschungsgesellschaft (DFG) within the Collaborative Research Center Transregio 123-Planar Optronic Systems. References [1] Ma H, Jen AKY, Dalton LR. Polymer-Based Optical Waveguides: Materials, Processing, and Devices. Adv. Mater 22;14(19): [2] Ishigure T, Nihei E, Koike Y. Graded-index polymer optical fiber for high-speed data communication. Appl Opt 1994; 33(19): [3] Matsuura T, Ishizawa M, Hasuda Y, Nishi S. Polyimides derived from 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl. 2. Synthesis and characterization of polyimides prepared from fluorinated benzenetetracarboxylic dianhydrides. Macromolecules 1992; 25(13): [4] Kurokawa T, Takato N, Katayama Y. Polymer optical circuits for multimode optical fiber systems. Appl Opt 198; 19(18): [5] Weinert A. Kunststofflichtwellenleiter, Grundlagen, Komponenten, Installation. Erlangen: Publicis-MCD-Verlag; 1998.p.11 [6] Hans-Dieter Bauer, Wolfgang Ehrfeld, Michael Harder, Thomas Paatzsch, Martin Popp, Ingo Smaglinski. Polymer waveguide devices with passive pigtailing: an application of LIGA technology. Synth. Metals 2; 115:13-2. [7] S. Sinzinger, J. Jahns. Microoptics. Weinheim: Wiley-VCH Verlag; 1999.p. 183.